Comfortable, oxygen permeable contact lenses and the manufacture thereof

ABSTRACT

Comfortable, oxygen permeable hard and semi-hard contact lenses are made from the copolymer of ethylenically unsaturated siloxanylalkoxy ester monomer, ethylenically unsaturated fluorocarbon ester monomer and ethylenically unsaturated sulfone monomer; the copolymer plastic can be modified by the incorporation of hardening, stability and wettability agents and methods for the manufacture thereof.

This is a division of application Ser. No. 153,811 filed Feb. 8, 1988,now U.S. Pat. No. 4,861,850 which in turn is a continuation-in-part ofapplication Ser. No. 880,668, filed June 30, 1986, which matured intoU.S. Pat. No. 4,743,106.

BACKGROUND OF THE INVENTION

Oxygen permeable contact lenses in the prior art are essentially madefrom siloxane monomer and methyl methacrylate. These lenses arepermeable to oxygen; hence, allowing oxygen from the air to pass throughthe lenses and reach the cornea which allows such lenses to be worn forlonger periods of time as compared to non-oxygen permeable contactlenses such as PMMA which are available previously.

Such contact lenses were disclosed in the prior art by Gaylord, U.S.Pat. Nos. 3,808,178 and 4,120,570. Later, Ellis disclosed in hispatents, U.S. Pat. Nos. 4,152,508 and 4,330,383, the partial replacementof the methyl methacrylate monomer with dimethyl itaconate. The Novickypatents, U.S. Pat. Nos. 4,216,303, 4,242,483, 4,248,989, 4,303,772 and4,365,074, disclosed contact lenses comprised of high molecular weightof polysiloxanylalkyl esters of acrylic and methacrylic acids. The Changpatent, U.S. Pat. No. 4,182,822, disclosed contact lenses comprised of acopolymer from polysiloxanylalkyl ester of acrylic and methacrylic acidessentially the same as disclosed in the Gaylord patents, supra., thatwere copolymerized with N-vinyl pyrrolidinone or N,N-dimethylmethacrylamide.

In Ichinoche, et al., Canadian Pat. No. 1,184,341, it teaches the use oforganosiloxanyl ester monomer of acrylic and methacrylic acidcopolymerized with fluorocarbon ester monomers of acrylic andmethacrylic acids and copolymerized to produce oxygen permeable contactlenses. The LeBoeuf patent, U.S. Pat. No. 4,246,389, discloses acrylicsiloxane based polymers which also contain HEMA and polyvinyl2-pyrrolidinone which are suitable for use in forming water-containingoxygen permeable contact lenses.

All siloxane ester monomers in the prior art employ essentially the samealkyl bridge between methacryloxy group and siloxanyl part of thestructure; wherein, neither one used ethoxy group or 2,3-dioxypropylgroups. The organosilicone monomers of the present invention can becopolymerized with perfluoroalkyl ester monomers and with sulfonemonomers.

SUMMARY OF THE INVENTION

The present invention relates to a novel and new generation of contactlenses comprising of copolymers made from siloxanylalkoxy ester monomersof acrylic, methacrylic, itaconic acids or mixtures thereof andperfluoroalkyl ester monomers of acrylic, methacrylic, itaconic acid ormixtures thereof which are copolymerized with ethylenically unsaturatedsulfone alkyl monomers and ethylenically unsaturated sulfone estermonomers of acrylic, methacrylic , itaconic acid or mixtures thereof, toproduce highly oxygen permeable and improved materials for contactlenses.

The first reprsentative siloxanylalkoxy ester monomer of acrylic ormethacrylic acid of the present invention has the general structuralformula: ##STR1## wherein X and Y are C₁ to C₆ alkyl, cyclic, phenylgroups or groups of the following structure: ##STR2## m being an integerfrom 1 to 5 and R is methyl group or hydrogen.

The second useful organosiloxanylalkoxy ester monomer of acrylic ormethacrylic acid is represented by the following structural formula:##STR3## n being an integer from 1 to 3; wherein, X and Y are C₁ to C₆alkyl, cyclic, phenyl groups or groups of the following structure:##STR4## m being an integer from 1 to 5 and R is methyl group orhydrogen.

The above disclosed new organosilicone monomers can be partiallysubstituted by additional organosiloxanylalkyl ester monomers from theprior art. The first representative partial substituteorganosiloxanylalkyl ester monomer of acrylic and methacrylic acid fromthe prior art has the structural formula: ##STR5## wherein, X and Y areC₁ to C₆ alkyl, cyclic, phenyl groups or groups of the followingstructure: ##STR6## m being an integer from 1 to 6, n being an integerfrom 1 to 3 and R is methyl group or hydrogen.

The second useful partial substitute organosiloxanylalkyl ester monomerof acrylic and methacrylic acids is represented by the followingformula: ##STR7## wherein, X and Y are C₁ to C₆ alkyl, cyclic, phenylgroups or groups of the following structure: ##STR8## m being an integerfrom 1 to 6, n being an integer from 1 to 3, A is selected from C₁ to C₆alkyl, cyclic or phenyl groups, R is methyl group or hydrogen and D ishydrogen or hydroxy group.

The third useful partial substitute organosiloxanylalkyl ester monomerof acrylic and methacrylic acids is represented by the followingstructural formula: ##STR9## wherein, X and Y are groups of thefollowing structure: ##STR10## m being an integer from 1 to 5, n is aninteger from 1 to 3, wherein, A is selected from C₁ to C₆ alkyl, cyclicor phenyl groups and R is methyl group or hydrogen.

The fourth useful partial substitute organosiloxanylalkyl ester monomerof itaconic acid is represented by the following formula: ##STR11##wherein, X and Y are C₁ to C₆ alkyl, cyclic, phenyl groups or groups ofthe following structure: ##STR12## m being an integer from 1 to 5, nbeing an integer from 1 to 3; wherein, A is selected from C₁ to C₆alkyl, cyclic or phenyl groups and Q is methyl group, hydrogen orhydroxy group.

The perfluoroalkyl ester monomers of acrylic and methacrylic acid arerepresented by the following formula: ##STR13## n being an integer from1 to 3, R is methyl group or hydrogen, m being an integer from 1 to 4, abeing an integer from 1 to 10 and Z is fluorine or hydrogen.

Another useful perfluoroalkyl ester monomer of the present invention isrepresented by the following formula: ##STR14## and telomer alcoholmethacrylates or acrylates of the following formula: ##STR15## m is aninteger from 1 to 5 and R is methyl group or hydrogen. Particularlyuseful in the manufacture of the lenses of the present invention arethose fluoroalkyl esters selected from the group consisting ofperfluoroalkylethyl acrylates and methacrylates of the followingformula: ##STR16## wherein, n is an integer from 1 to 10 and R is methylgroup or hydrogen.

The perfluoroalkyl ester monomers of itaconic acid useful in the presentinvention for the manufacturing of contact lenses are represented by thefollowing formula: ##STR17## R is alkyl group or group of the followingstructure: ##STR18## n being an integer from 1 to 4 and m is an integerfrom 1 to 10.

Additional perfluorocarbon monomers useful in the present invention toform copolymers are found in the European Patent Application No. 0084406by David E. Rice, et al., such monomers having the following generalstructural formula:

    A-CF.sub.2 -O-(CF.sub.2 -CF.sub.2 O).sub.m -(CF.sub.2 O).sub.n -CF.sub.2 Z

wherein, m is an integer from 2 to 20, n is an integer from 2 to 30, Ais selected from CF₃ --, CH₃ --, CH₂ F--, and CF₂ H--, and Z has theformula which includes one of the following: ##STR19## or mixturesthereof.

The principal sulfone monomers embodied in the present invention whichcontribute to the increased oxygen permeability and biocompatiability ofthe copolymer for contact lenses are represented by the followinggeneral formula: ##STR20## wherein, A is selected from one of thefollowing: ##STR21## wherein, Q is C₁ to C₂₀ alkyl, perfluoroalkyl,cyclic or phenyl groups and n is an integer from 1 to 5, organosulfonemonomers having the following formula: ##STR22## wherein R₁ and R₂ arehydrogen, alkyl, cyclic or phenyl groups, n is an integer from 1 to 5and m is an integer from 0 to 10.

The preferable sulfone monomers which are useful in the presentinvention are:

methyl vinyl sulfone,

meth;yl styrene sulfone,

ethyl vinyl sulfone,

ethyl styrene sulfone,

propyl vinyl sulfone,

propyl styrene sulfone,

phenyl vinyl sulfone,

phenyl styrene sulfone,

cyclohexyl vinyl sulfone,

cyclohexyl styrene sulfone,

pentyl vinyl sulfone,

pentyl styrene sulfone,

butyl vinyl sulfone,

butyl styrene sulfone,

phenoxyethyl vinyl sulfone,

phenoxyethyl styrene sulfone,

divinyl sulfone,

methacryloxyethyl methyl sulfone,

methacryloxyethyl ethyl sulfone,

methacryloxyethyl propyl sulfone,

methacryloxyethyl butyl sulfone,

methacryloxyethyl phenyl sulfone,

methacryloxyethyl pentyl sulfone,

methacryloxyethyl styrene sulfone,

2-(N ethylperfluoroalkylsulfonamido)ethylmethacrylate,

2-(N ethylperfluoroalkylsulfonamide)ethylacrylate,

or mixtures thereof.

The copolymer plastic material of the present invention alsoincorporates hardening agents such as methyl methacrylate, ethylmethacrylate, propyl methacrylate, cyclohexyl methacrylate, glycidylmethacrylate, phenoxyethyl methacrylate, phenyl methacrylate,tetrahydrofurfuryl methacrylate, methyl acrylate, ethyl acrylate, propylacrylate, cyclohexyl acrylate, phenoxyethyl acrylate, phenyl acrylate,tetrahydrofurfuryl acrylate, dimethyl itaconate, diethyl itaconate,dipropyl itaconate, dicyclohexyl itaconate, diphenyl itaconate, vinylbenzene (styrene, divinyl benzene or mixtures thereof.

The contact lens material is further modified by the incorporation ofwettability and cross-linking agents to improve overall performance ofthe contact lens on the human eye. Such representative monomers ofwettability agents are acrylic acid, methacrylic acid, 2-hydroxyethylacrylate, 2-hydroxyethyl methaarylate, 2,3-dihydroxypropyl acrylate,2,3-dihydroxypropyl.

Representative cross-linking agents are ethyleneglycol dimethacrylate,diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate,tetraethyleneglycol dimethacrylate, dimethacrylate siloxanyl estermonomer (PSX-563A), ethyleneglycol diacrylate, diethyleneglycoldiacrylate, triethyleneglycol diacrylate, tetraethyleneglycoldiacrylate, divinyl benzene, divinyl sulfone, trimethylolpropanetrimethacrylate or mixtures thereof.

A variety of other ingredients may be included in the polymerizationmixture so that to either enhance or provide specific properties. Forexample, wettability of the surface of the lens is a very importantcharacteristic for contact lenses to possess in order to providedcomfort and good visual acuity. In addition to already disclosedwettability agents named herein, additional ethylenically unsaturatedmonomers can also be incorporated that have a hydrophilic group such ashydroxy, carboxy, carbonamido sulfonyl, and sulfonamido groups. As anexample, it can be 2-carboxyethyl acrylate, 2-carbonamidoethylmethacrylate, 2-sulfonethyl methacrylate, 2-sulfonamidoethyl acrylate,vinyl sulfonic acid, or mixtures thereof.

The preferred composition of the present invention comprises of:

(a) from about 5 to 65 weight percent of ethylenically unsaturatedorganosiloxanylalkoxy ester monomer of acrylic or methacrylic acid andsiloxanylalkyl ester monomers of itaconic acid or mixtures thereof;

(b) from about 2 to 40 weight percent of ethylenically unsaturatedperfluoralkyl ester monomer or mixtures thereof;

(c) from about 2 to 40 weight percent of ethylenically unsaturatedsulfone monomer or mixtures thereof;

(d) from about 10 to 70 weight percent of hardening agent monomer(preferably, methyl methacrylate, cyclohexyl methacrylate, dimethylitaconate) or mixtures thereof;

(e) from about 1 to 18 weight percent of difunctional cross-linkingmonomer (preferably triethyleneglycol dimethacrylate,tetraethyleneglycol dimethacrylate) or mixtures thereof; and

(f) from about 1 to 15 weight percent of wetting agent monomer(preferably methacrylic acid or N-vinyl 2-pyrrolidinone) or mixturesthereof.

The copolymer plastic can also be prepared without perfluoralkyl estermonomer and the material would still possess high oxygen permeabilityand good wettability.

The polymerization of the oxygen permeable material for the manufactureof contact lenses disclosed in the present invention is accomplished byusing free-radical polymerization, such techniques are disclosed in theprior art.

EXAMPLE 1

This example illustrates the preparation oftris(trimethylsiloxy)methacryloxyethoxysilane, an organosilicone monomeruseful in the present invention. To a three-necked, round bottom, 12liter flask equipped with mechanical stirrer and cooling system is added5 liters of dry toulene, 2 moles of 2-hydroxyethylmethacrylate and 2moles plus 10% excess of triethylamine. The flask content is cooled downto about 5° C. When the temperature is reached, start addition of 2equivalent moles of tris(trimethylsiloxy)chlorosilane; all additiontakes about one hour. Then the temperature is raised to 30° C. and thestirring is continued for 6 hours. After the reaction is completed, thewhite precipitation of triethylamine hydrochloride is filtered off;distillation of toulene proceeds at about 45° C. under aspirator vacuum.The crude product is washed twice with cold water and then 2 times with5% sodium bicarbonate solution; the the crude product is washed again 2times with cold water. The crude product is dried over anhydrous MgSO₄for 3 hours. The MgSO₄ is removed by filtration and the product isstripped under high vacuum at 75° C. The refractive index n_(D) ²⁵ is1.4112±0.001; the infrared spectrum confirmed the structure. The sameprocedure is used for the preparation oftris(pentamethyldisiloxanyl)methancryloxyethoxysilane,bis(pentamethyldisiloxanyl)trimethylsiloxanylmethacryloxyethoxysilane,and bis(trimethylsiloxy)pentamethyldisiloxanylmethacryloxyethoxysilaneif the starting material tris(trimethylsiloxy)chlorosilane is replacedwith pentamethylchlorosilane and trimethylchlorosilane in the desiredmolar ratio.

EXAMPLE 2

This example illustrates the preparation of the representativeperfluoroalkyl ester monomer useful in the present invention. A 12liter, 3-necked, round bottom flask equiped with a mechanical stirrerand cooling system is charged with 5 liters of toulene, 3 moles of1,1',2,2'-tetrahydroperfluorohexylethanol and 3 moles plus 10% excess oftriethylamine. The flask content while stirring is cooled down to about5°-10° C. until the temperature is reached, then start addition of 1mole of trichloromethacryloxypropylsilane; all addition takes about onehour. When all addition is completed the temperature of the reactionmixture is raised to 30° C. and stirring is continued for 10 hours.After the reaction is completed white precipitation of triethylaminehydrochloride is filtered off; distillation of toulene proceeds at about45° C. under aspirator vacuum. The crude product is washed twice withcold water, then 2 times with 5% sodium bicarbonate solution and thenthe crude product is washed again 2 times with cold water. The crudeproduct is dried over anhydrous MgSO₄ for 3 hours; the MgSO₄ is removedby filtration and the product is stripped under high vacuum at 75° C.The monomer is then ready to be used in the polymerization process. Manyadditional tris(perfluoroalkylethoxy)methacryloxypropylsilanes can beprepared by this chemistry.

EXAMPLE 3

This example is an illustration of the preparation of2,3-di[tris(trimethylsiloxy)siloxanyl]methacryloxypropane. The 12 literflask equipment with a mechanical stirrer, additional funnel and coolingsystem is charged with 5 liters of toulene, 2 moles of2,3-dihydroxypropylmethacrylate and 2 moles plus 10% excess oftriethylamine. The contents of the flask is cooled down to 5° C., thenaddition of 2 moles of tris(trimethylsiloxy)chlorosilane proceeds inabout a period of one hour. When all addition is completed thetemperature of the reaction mixture is elevated to 30° C. and stirringis continued for about 8 hours. After the reaction is completed, whiteprecipitation of triethylamine hydrochloride is filtered off;distillation of toulene proceeds at about 45° C. under aspirator vacuum.The crude product is washed twice with cold water and 2 times with 5%sodium bicarbonate solution and then the crude product is washed again 2times with cold water. The crude product is dried over anhydrous MgSO₄for 3 hours; the MgSO.sub. 4 is removed by filtration and the product isstripped under high vacuum at 75° C. The refractive index of the productis 1.4083±0.002. The same procedure is used for the preparation of2,3-di(pentamethyldisiloxanyl)methacryloxypropane if the startingmaterial tris(trimethylsiloxy)chlorosilane is replaced withpentamethylchlorodisiloxane.

EXAMPLE 4

This example illustrates the preparation of representative copolymermaterial for contact lenses. To a 200 mol flask is added 35 grams oforganosilicone monomer previously prepared in Example 1,tris(trimethylsiloxy)methacryloxyethoxysilane, 15 grams of2,3-di[tris(trimethylsiloxy)siloxanyl]methacryloxypropane, 2 grams ofmethacrylate dimer (PSX-563A), 10 grames of cyclohexyl methacrylate, 5grams of methacrylic acid, 2.5 grams of N-vinyl 2-pyrrolidinone, 5 gramsof perfluoro monomer prepared in Example 2, 10 grams oftriethyleneglycol dimethacrylate, 14 grams of methyl methacrylate, 5drops of D&C #6 color dye, 0.5 ml of t-butyl peroxypivalate and 0.2grams of benzoyl peroxide. All contents are mixed thoroughly and pouredinto polypropylene tubes, molds or sililated glass tubes, closed andpolymerized in water bath at 40° C. for a period of about 18 hours. Therods are then put into a thermostated oven for at least 24 hours, havinga temperature of about 100° C. The copolymer plastic is transparent,hard and suitable for the machining of highly permeable contact lenses.

EXAMPLE 5

This example illustrates the preparation of representative copolymerplastic material for contact lenses made only from siloxanyl monomer asa source of oxygen permeability. To the 200 ml flask is added 41 gramsof 2,3,-di[tris(trimethylsiloxy)siloxanyl]methacryloxypropane, 10 gramsof cyclohexyl methacrylate, 4.5 grams of methacrylic acid, 5 grams ofdiethyleneglycol dimethacrylate, 39 grams of methyl methacrylate, 0.4grams of t-butyl peroxyoctoate and 0.1 grams of benzoyl peroxide, allcomponents are mixed thoroughly and poured into polypropylene tubes,molds or sililated glass tubes closed with stoppers and polymerized in awater bath or thermostated oven set at 45° C. for a period of about 20hours. The rods or blanks are then put into a thermostated ovenpreheated at 105° C. for a period of 24 hours. The copolymer plastic istransparent, hard, oxygen permeable, wettable and suitable formanufacturing oxygen permeable contact lenses.

EXAMPLE 6-13

This example illustrates the preparation of optically clear plasticprepared in accordance with the polymerization procedure described inExample 5, except the amounts and kinds of monomers may be different asshown in the following table:

                  TABLE                                                           ______________________________________                                                       Example Number                                                 Components (Parts)                                                                             6     7     8   9   10  11  12  13                           ______________________________________                                        2,3-di[tris(trimethylsiloxy)-                                                                  35    30    20  10  0   15  20  20                           siloxanyl]methacryloxypropane                                                 tris(trimethylsiloxy)-                                                                         0     10    20  30  40  0   15  15                           methacryloxyethoxysilane                                                      tris(dimethylhydrosiloxy)-                                                                     5     0     5   0   10  15  5   l0                           methacryloxypropylsilane                                                      methacryloxymethylpenta-                                                                       0     5     0   0   0   15  5   0                            methyldisiloxane                                                              cyclohexyl methacrylate                                                                        12    10    5   0   10  6   10  0                            dimethyl itaconate                                                                             10    5     20  20  0   10  0   30                           triethyleneglycol                                                                              6     8     7   5   4   l0  6   8                            dimethacrylate                                                                methyl methacrylate                                                                            25    28    30  30  25  30  40  0                            methacrylic acid 5     45    0   5   4   6   0   4                            N-vinyl 2-pyrrolidinone                                                                        3     0     6   0   3   0   5   2                            vinyl benzene    0     5     0   3   4   10  0   10                           ______________________________________                                    

EXAMPLE 14

This example illustrates the preparation of oxygen permeable copolymerplastic for contact lenses made from siloxanylalkoxy ester monomer andperfluoroalkyl ester monomer as a source of oxygen permeability. To a200 ml flask is added 35 parts ofbis(pentamethyldisiioxanyl)trimethylsiloxymethacryloxyethoxysilane, 15parts of cyclohexyl methacrylate, 10 parts oftris(1,1'-dihydroperfluorohexyloxy)methacryloxypropylsilane, 3 parts ofN-vinyl 2-pyrrolidinone, 7 parts of tetraethyleneglycol dimethacrylate,5 parts of methacrylic acid, 25 parts of methyl methacrylate, 0.5 partsof t-butyl peroxypivalate and 0.2 parts of benzoyl peroxide; thepolymerization is carried out by the same procedure as described inExample 5. The resulting plastic is transparent, hard, stable, wettableand suitable for machining of highly permeable contact lenses.

EXAMPLE 15-22

Samples of optically clear plastic are prepared in accordance with thepolymerization procedure described in Example 14, except the amounts andkinds of components may be different, as shown in the following table:

                  TABLE                                                           ______________________________________                                                       Example Number                                                 Components (Parts)                                                                             15    16    17  18  19  20  21  22                           ______________________________________                                        tris(1,1'-dihydroperfluoro-                                                                    l0    0     5   20  40  0   20  15                           hexyloxy)methacryloxypropyl-                                                  silane                                                                        bis(1,1',2,2'-tetrahydro-                                                                      0     15    5   0   0   5   3   5                            perfluorobutyl)itaconate                                                      2,3-di[tris(trimethylsiloxy)-                                                                  30    25    10  20  20  5   0   10                           siloxyanyl]methacryloxy-                                                      propane                                                                       tris(trimethylsiloxy)meth-                                                                     10    15    25  5   0   30  40  20                           acryloxyethoxysilane                                                          di(pentamethyldisiloxanyl-                                                                     5     0     5   10  5   5   5   8                            ethyl)itaconate                                                               dimethyl itaconate                                                                             10    0     6   10  30  15  0   12                           methyl methacrylate                                                                            20    30    18  10  10  20  18  20                           cyclohexyl methacrylate                                                                        l0    15    8   20  0   0   15  0                            methacrylic acid 3     4     5   1   3   5   3   6                            N-vinyl 2-pyrrolidinone                                                                        0     3     2   6   2   0   4   0                            vinyl benzene    0     2     6   0   3   8   0   0                            diethyleneglycol 6     0     2   4   6   0   0   1                            dimethacrylate                                                                triethyleneglycol                                                                              0     6     3   4   0   6   10  6                            dimethacrylate                                                                ______________________________________                                         *All samples of the above copolymer plastic are clear, transparent and ga     permeable.                                                               

EXAMPLE 23

This example illustrates the preparation of oxygen permeable copolymerplastic for contact lenses from siloxanylalkoxy ester of methacrylicacid and sulfone monomer as a source of oxygen permeability; consistingof 40 parts of tris(trimethylsiloxy) methacryloxyethoxysilane, 10 partsof cyclohexyl methacrylate, 8 parts of methyl vinyl sulfone, 20 parts oftetrahydrofurfuryl methacrylate, 5 parts of 2-hydroxyethyl methacrylate,7 parts of N-vinyl 2-pyrrolidinone, 7 parts of methyl methacrylate and0.4 parts of t-butyl peroxypivalate are polymerized. The resultingcopolymer plastic has a hardness of 86±2 as

EXAMPLE 24

A contact lens has been manufactured from the oxygen permeable materialof the present invention using standard, conventional manufacturingtechniques known in the art. The base curve of the lens was cut at 7.80mm, the front curve of the lens was cut at 8.21 mm, the center thicknessof the lens was 0.19 mm. The contact lens was then polished using atechnique widely known in the contact lens industry. The base curve ofthe lens was 7.81 mm; after the lens was polished the base curveremained at 7.81 mm. The lens was soaked over 72 hours in Soaclenssolution and the base curve remained at 7.81 mm.

EXAMPLE 25-32

Samples of optically clear plastic are prepared in accordance with thepolymerization procedure described in Example 4, except the amounts andkinds of components may be different as shown in the following table:

    ______________________________________                                                       Example Number                                                 Components (Parts)                                                                             25    26    27  28  29  30  31  32                           ______________________________________                                        tris(trimethylsiloxy)                                                                          25    40    30  40  30  45  10  0                            methacryloxyethoxysilane                                                      tris(trimethylsiloxy)-                                                                         10    0     10  5   10  0   20  30                           methacryloxypropylsilane                                                      1,1',2,2'-tetrahydroper-                                                                       l0    5     0   10  2   0   5   0                            f1uorohexyl methacrylate                                                      tris(1,1'-dihydroperfluoro-                                                                    5     0     5   0   2   10  0   20                           butyloxy)methacryloxy-                                                        propylsilane                                                                  methyl vinyl sulfone                                                                           0     5     6   0   10  0   10  10                           methyl methacrylate                                                                            30    30    29  30  21  35  30  15                           cyclohexyl methacrylate                                                                        l0    l0    11  10  10  0   10  15                           methacrylic acid 5     5     4   2   5   5   5   4                            diethyleneglycol 5     5     5   3   10  5   10  6                            dimethacrylate                                                                ______________________________________                                    

EXAMPLE 33

The polymerizationof a mixture of 20 parts of2,3-di[tris(trimethylsiloxy)siloxanyl]methacryloxypropane, 20 parts oftris(trimethylsiloxy)methacryloxypropylsilane, 10 parts ofbis(1,1',5-trihydroperfluoropentyl)itaconate, 10 parts of cyclohexylmethacrylate, 8 parts of ethyleneglycol dimethacrylate, 4 parts ofmethacrylic acid, 3 parts of N-vinyl 2-pyrrolidinone and 25 parts ofmethyl methacrylate are polymerized by using free-radical catalysts, asshown in Example 5, in polypropylene base curve premolded caps. Theresulting plastic gives a transparent, concave plug.

EXAMPLE 34

The polymerization procedure of Example 5 is repeated, except theamounts and kinds of components in the polymerization are changed asfollows: 45 parts oftris(trimethylsiloxy)siloxanylmethacryloxyethoxysilane, 10 parts oftris(1,1',2,2'-tetrahydroperfluoropentyloxy) methacryloxypropylsilane,10 parts of cyclohexyl methacrylate, 9 parts of triethyleneglycoldimethacrylate, 5 parts of methacrylic acid, 3 parts of N-vinyl2-pyrrolidinone and 18 parts of methyl methacrylate are polymerized byusing free-radical initiator at 47° C. The plastic is then removed fromthe molds, transferred into a thermostated oven which is set at 108° C.and the copolymer plastic is cured for an additional 24 hours. Theresulting plastic has an oxygen permeability of about 91×10⁻¹¹ (cm²/sec)(ml O₂ /ml×mm Hg) at 35° C., as analyzed on the Schema-VersataeModel #920 instrument

EXAMPLE 35

The polymerization procedure of Example 5 is repeated, except theamounts and kinds of components in the polymerization are changed asfollows: 35 parts oftris(trimethylsiloxy)siloxanylmethacryloxypropylsilane, 20 parts oftris(perfluoroalkylethoxy) methacryloxypropylsilane (which can beprepared by chemistry disclosed in Example 2), 15 parts ofcyclohexylmethacrylate, 10 parts of triethyleneglycol dimethacrylate, 6parts of methacrylic acid and 3 parts of N-vinyl pyrrolidinone which arepolymerized using free-radical initiator in suitable polypropylene moldsin constant temperature water bath at 45° C. for about 24 hours; theplastic is then removed from the water bath and placed in thermostatedoven preheated to 105° C., where the process of final polymerizationproceeds over a 24 hour period. The resulting plastic is removed, cut tothe shape of a contact lens by conventional technique known in thecontact lens industry and machined to a prescription contact lens ofhigh oxygen permeability.

EXAMPLE 36

The polymerization procedure of Example 5 is repeated, except theamounts and kinds of components in the polymerization are changed asfollows: 35 parts of tris(hydrodimethylsiloxy)methacryloxypropysilane,20 parts of tris(perfluoroalkylethoxy)methacryloxypropylsilane (whichcan be prepared the same as in Example 2), 15 parts of cyclohexylmetharylate, 10 parts of triethyleneglycol dimethacrylate, 6 parts ofmethacrylic acid constant temperature water bath at 45° C. for about a24 hour period; the plastic is then removed from water bath and placedin thermostated oven preheated to 105° C. The process of finalpolymerization proceeds within a 24 hour period. The resulting plasticis removed, cut to the shape of a contact lens by the conventionaltechnique known in the contact lens industry and machined to aprescription contact lens of high oxygen permeability.

EXAMPLE 37

The polymerization of a mixture of 20 parts oftris(trimethylsiloxy)methacryloxyethoxysilane, 20 parts of 2-(Nethylperfluoroalkylsulfonamido)ethylmethacrylate, 10 parts oftris(trimethylsiloxy)methacryloxypropylsilane, 10 parts of cyclohexylmethacrylate, 8 parts of ethyleneglycol dimethacrylate, 4 parts ofmethacrylic acid, 3 parts of N-vinyl 2-pyrrolidinone, and 25 parts ofmethyl methacrylate are polymerized by using a free-radical catalyst, asshown in Example 5, in polypropylene base curve premolded caps. Theresulting plastic gives a transparent, concave plug suitable for themanufacture of an oxygen permeable contact lens.

The embodiments of the invention which are claimed as an exclusiveproperty or priviledge are defined as follows:
 1. An ophthlamic deviceformed of a copolymer plastic material which comprises:at least oneorganosilicone monomer selected from the group consisting of(1) anorganosiloxanylalkoxy ester monomer of acrylic or methacrylic acidhaving the following structural formula: ##STR23## wherein X and Y areC₁ to C₆ alkyl, phenyl or groups of the following structure: ##STR24##wherein A is C₁ -C₆ alkyl or phenyl, m being an integer from 1 to 5 andR is methyl or hydrogen; and, (2) an organosiloxanylalkoxy ester monomerof acrylic or methacrylic acid having the following structural formula:##STR25## n being an integer from 1 to 3, wherein A, X, Y, R and m areas defined above; which are copolymerized with an organosulfone monomerhaving the general structural formula: ##STR26## wherein R₁ is selectedfrom one of the following: ##STR27## wherein Q is C₁ to C₂₀ alkyl,perfluoroalkyl, or phenyl and g is an integer from 1 to
 5. 2. Theophthalmic device of claim 1 wherein the copolymer plastic also includesa hardening agent selected from the group consisting of alkyl estermonomers of acrylic, methacrylic and itaconic acids and mixturesthereof.
 3. The ophthalmic device of claim 1 wherein the copolymerplastic also includes at least one wettability agent selected from thegroup consisting of acrylic acid, methacrylic acid, 2-hydroxyethylacrylate, 2-hydroxyethyl methacrylate, 2,3-dihydroxypropyl acrylate,2,3-dihydroxypropyl methacrylate, N-vinyl 2-pyrrolidinone and mixturesthereof.
 4. The ophthalmic device of claim 1 wherein the copolymerplastic also includes at least one cross-linking agent selected from thegroup consisting of ethyleneglycol dimethacrylate, diethyleneglycoldimethacrylate, triethyleneglycol dimethacrylate, tetraethyleneglycoldimethacrylate, dimethacrylate siloxanyl ester monomer, ethyleneglycoldiacrylate, diethyleneglycol diacrylate, triethyleneglycol diacrylate,tetraethyleneglycol diacrylate, divinyl benzene, divinyl sulfone,trimethylolpropane trimethacrylate and mixtures thereof.
 5. An oxygenpermeable contact lens material comprising at least one monomer selectedfrom the group consisting of organosiloxanylalkyoxy ester monomershaving the following formula: ##STR28## wherein X and Y are C₁ to C₆alkyl, phenyl or groups of the following structure: ##STR29## wherein Ais C₁ -C₆ alkyl or phenyl, m being an integer from 1 to 5 and R ismethyl or hydrogen; and, ##STR30## n being an integer from 1 to 3,wherein A, X, Y, R and m are as defined above;which are copolymerizedwith an organosulfone monomer for the purpose of increasing oxygenpermeability, said organosulfone monomer having the following structuralformula: ##STR31## wherein R₁ is selected from one of the following:##STR32## wherein Q is C₁ to C₂₀ alkyl, perfluoroalkyl, or phenyl and gis an integer from 1 to 5; said copolymer plastic including: at leastone hardening agent selected from the group consisting of alkyl estermonomers of acrylic, methacrylic and itaconic acids and mixturesthereof; a wettability agent selected from the group consisting ofacrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethylmethacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropylmethacrylate, N-vinyl 2-pyrrolidinone and mixtures thereof; and across-linking agent selected from the group consisting of ethyleneglycoldimethacrylate, diethyleneglycol dimethacrylate, triethyleneglycoldimethacrylate, tetraethyleneglycol dimethacrylate, dimethacrylatesiloxanyl ester monomer, ethyleneglycol diacrylate, diethyleneglycoldiacrylate, triethyleneglycol diacrylate, tetraethyleneglycoldiacrylate, divinyl benzene, divinyl sulfone, trimethylolpropanetrimethacrylate and mixtures thereof.